Enantioselective Synthesis of Sterically Hindered Tertiary α-Aryl Oxindoles via Palladium-Catalyzed Decarboxylative Protonation. An Experimental and Theoretical Mechanistic Investigation

Identifier:  imarina:4123847

Handle: https://hdl.handle.net/20.500.11797/imarina4123847

Authors:  Biosca, M; Jackson, M; Magre, M; Pàmies, O; Norrby, PO; Diéguez, M; Guiry, PJ

Abstract:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim We have developed the first catalytic asymmetric preparation of sterically hindered tertiary α-aryl oxindoles via enantioselective palladium-catalyzed decarboxylative protonation of the corresponding α-aryl-β-amido allyl esters. The reaction occurs under very mild conditions and in short reaction times, providing excellent yields and promising enantioselectivities (ee's up to 78%). We have also performed an experimental investigation of the reaction mechanism and employed theoretical calculations to understand the nature of the enantioselectivity-determining step. (Figure presented.).